Anti-Electrostatic Anion-Anion Noncovalent Interactions Are Not Halogen Bonds: Evidence from X···O Contacts in XO4− Dimers and Oligomers in Crystals Structures

Abstract

This study investigates anion–anion assemblies involving perhalate anions, XO4− (X = Cl, Br, I), in crystal structures retrieved from the Cambridge Structural Database to clarify the nature of the intermolecular interactions frequently interpreted as halogen bonds. Molecular electrostatic surface potential analysis demonstrates that isolated XO4− anions do not exhibit electrophilic σ-holes on the halogen or oxygen atoms along the O–X bond extensions, thereby precluding their role as conventional halogen- or chalcogen-bond donors. Gas-phase calculations further show that direct anion–anion assemblies are intrinsically repulsive and unstable in isolation. However, when dielectric screening is introduced through implicit solvation models, metastable dimeric and oligomeric arrangements consistent with crystallographic motifs become accessible. Complementary QTAIM, IGMH, NBO, and SAPT analyses show that the observed X···O and O···O contacts are weak, environment-assisted anti-electrostatic interactions arising from a combination of dielectric screening, polarization, dispersion, and donor–acceptor contributions. The results demonstrate that the structural organization of perhalate anions in crystalline environments is governed primarily by collective environmental and crystal-packing effects rather than intrinsic attractive interactions between isolated anions.